TW483292B - Electrolytic copper foil - Google Patents

Abstract

An object of the present invention is to provide a copper foil having excellent adhesion to an etching resist layer, without performing physical polishing such as buffing in pre-treatment of an etching process to form a circuit from the copper foil. To attain the object, in electroforming, a titanium oxide material having a grain size number of 6.0 or more is employed as a copper deposition surface of the rotating drum cathode, and glue and/or gelatin is added in an amount of 0.2-20 mg/l to a copper sulfate solution, thereby producing a drum foil. An electrodeposited copper foil obtained from the drum foil, in which 20% or more of the crystals present in a shiny side surface of the electrodeposited copper foil have a twin-crystal structure, is used for producing copper-clad laminates.

Description

483292 t483292 t

以及銅箔基 五、發明說明⑴ 一 發明領域： 本發明係有關於電解銅箔及其製造方法 層板。 習知技術說明： 銅二哥電氣、電子產業中最常使用在印刷電路板 衣程的基礎材#。-般來說，㈣是以熱壓成形的 ^於玻璃環氧（glass —ep〇xy)|#、笨紛（phen〇i)基材、、 聚亞酿胺（polyimide)蓉夕客八2 ^ 妓& Λ &、/ QeJ寻之问刀子絕緣基#上，作成鋼鶴 積層板，而被用於印刷電路板製造中。 5近年來，電子電機機器的體積越來越小，因此斜 於：臧式=積層板以及印刷電路板的體積縮小化，也； 越，越要，：了。為了要滿足這需求，銅羯積層板的多層化 、印刷電路2電路的微細化，便成為近來研究的重點了。 於$ 5 〇 # m到8 0 # m間距（p i t c h )的微細迴路的印 刷電路板而言，在蝕刻迴路前的光阻層被覆（resis^a^ on)工程是非常重要的。也就是說，為了在蝕刻迴路後， 保有良好的銅箱迴路斷面的深寬比（aspect rati〇)，·就必 須在蝕刻前形成良好狀態的光陴層。 、 ^ 了要得到良好的印刷電路板微細電路，在蝕刻方面 的對策有：①把先阻層更薄膜化，而使蝕刻液的供給更平 順’並採用液體光阻或電著光阻來取代乾薄膜^丨 。②為了不讓光阻層和銅箔層之間產生介面剝離，在銅箱 表面上施以拋光（buff )研磨等的物理研磨或化學研磨等處 理吏銅癌表面形成一定的凹凸狀，而使該介面的密著性And copper foil base 5. Description of the invention ⑴ Field of the invention: The present invention relates to an electrolytic copper foil and a method for manufacturing the same. Known technical description: The second material used in the electrical and electronic industries of copper is the most commonly used base material for printed circuit boards. -Generally speaking, ㈣ is formed by hot pressing glass-ep〇xy | #, phen〇i substrate, polyimide Rong Xi Ke 8 2 ^ Prostitute & Λ &, / QeJ Xunzhiwen knife insulation base #, made of steel crane laminates, and used in the manufacture of printed circuit boards. 5 In recent years, the size of electronic motor machines is getting smaller and smaller, so it is inclined to: Zang-style = the volume of laminated boards and printed circuit boards has been reduced, the more, the more, the more: In order to meet this demand, the multilayering of copper-clad laminates and the miniaturization of printed circuit 2 circuits have become the focus of recent research. For a printed circuit board with a fine circuit of $ 5 〇 # m to 8 0 # m pitch (pi t c h), the photoresist layer covering (resis ^ a ^ on) process before the etching circuit is very important. In other words, in order to maintain a good aspect ratio of the cross section of the copper box circuit after etching the circuit, it is necessary to form a good photocathode layer before etching. In order to obtain a fine printed circuit board fine circuit, the countermeasures in etching are: ① make the first resistive layer thinner and make the supply of etching solution smoother; and use liquid photoresist or electrophotographic photoresist to replace Dry film ^ 丨. ② In order to prevent interface peeling between the photoresist layer and the copper foil layer, the surface of the copper box is subjected to physical polishing such as buff polishing or chemical polishing, etc. The surface of the copper cancer is formed into a certain uneven shape, so that Interface adhesion

483292 五、發明說明（2) 可向上提升 究蝕刻液的 但是’ 質對應形成 刻時間、不 而這些方法 特別是 ，及有關於 的技術領域 當地少，機 然而在 電路板時’ 行曝光光阻 話，本來應 象發生，因 重要。 例如， 若不注意該 迴路斷線不 並努力研 域，可實 、縮短餘 寬比，然 著性問題 ，跟其他 究事例相 距的印刷 ，之後進 部分的 剝離的現 就變得很 ③〜擇適合蝕刻生產線的蝕刻液， 喷灑環（showe卜ri ) 關於在製造印刷電』^ 寸術’ 微細迴路的對d，.刻銅荡領 惡化钕刻料後的㈣迴路斷面的^ ::的其他對策卻幾乎沒有被想過。 ::於銅猪表面和光阻成份之間的资 有機材料和無機材料之間的介面問rs 比較起來，關於該介門 ^ 桃广 ,· x "由問4原本的研 構（mechamsm)方面也不太明晻。 現實上’要製造具有50 _到8〇_間 如果先在銅箔表面上带成 上形成蝕刻光阻層 圖案，再進行顯像以去除 :密著殘留在銅箱上的光阻層便ί; 在7C阻層和銅箔層之間的介面密著性 應該殘留的光阻層即蚀古 勺鲐相〶二π丄 即使有一點點的剝離，而且 ,..m 2幻泠蝕刻迴路的話，就會成為 艮的原因，也舍你 霄〜Ρ刷電路板的製造良率降低 而 且’就鼻"ϋ刻後銅综泡攸/ 合t π # # # β I 1 路沒有斷線，該銅箔迴路也 會有迴路寬度減少的問題發生。太 技括、n Ad, x王在檢查迴路時，雖然沒有 發線^通不良的j品，但是跟两 七七、^ ^ ^ 疋跟周圍的迴路比較起來，若存 刀 这部分的阻值會變高 因此483292 V. Description of the invention (2) The etching solution can be lifted upwards, but the quality of the corresponding etching time, but these methods are especially, and there are few relevant technical fields, but when the circuit board is used, the exposure photoresist Then, it should have happened because of importance. For example, if you do not pay attention to the circuit disconnection and work hard to study the area, you can reduce the width-to-width ratio. However, the problem of printing is separated from other cases, and the peeling of the next part becomes very difficult. Etching solution suitable for etching production line, spraying ring (showe bur) About the d of the fine circuit in the manufacture of printed electronics ^^ inch technology 'fine circuit, d .. engraved copper ring collar deteriorated after the neodymium etched section of the ㈣ circuit section ^ :: The other countermeasures were hardly thought of. :: Compare the interface between organic materials and inorganic materials on the surface of copper pigs and photoresist. In comparison, about this interface ^ Tao Guang, · x " by Question 4 original mechamsm It's not too bright. In reality, if you want to make a photoresist layer with a thickness of 50 mm to 80 mm, you can form an etched photoresist layer on the surface of the copper foil, and then develop it to remove it: the photoresist layer adhered to the copper box will be lit. ; The photoresist layer that should be left between the 7C resist layer and the copper foil layer is the photoresist layer, which is etched. Even if it is peeled a little, and ..m 2 magic etching circuit, It will be the cause of the problem. Also, the manufacturing yield of the P-brushed circuit board is reduced and the copper composite foam is etched after engraving. / #T # # # β 1 There is no disconnection in the circuit. The Copper foil circuits also suffer from reduced circuit widths. Taiji Kuo, n Ad, x Wang, while checking the circuit, did not send a wire j bad j product, but compared with two seven seven, ^ ^ ^ 疋 compared with the surrounding circuit, if the resistance value of this part of the knife Will get higher therefore

2169-3598-PF.ptd 胃6頁 在有迴路寬度有變窄的部分，兮2169-3598-PF.ptd page 6 of the stomach

五、發明說明（3) 名把這種印刷電路板裝在電機製品内使用時，由於阻值古 的部分發熱量較高，會使得銅箔迴路急速劣化5而提呈^ 化而損壞。這個結果可知，該印刷電路板只要稍受到一點 ，擊就會突然斷線，而造成電機製品等的動作突然 “、 圖式簡單說明： 、 』一。 =1圖係顯示電觫銅箔之示意剖面圖。第2圖係顯示電 鋼&之製造工程的概念示意圖。第3圖係顯示比較 鈿^科的結晶粒度圖。第4圖係顯示不具雙晶結構的電解 曰1 2 3 4 = ^ΤΕΜ衫像圖及電子線折射影像圖。第5圖係顯示呈雙 Ξ = Ξ的Ϊ解銅箱的ΤΕΜ影像圖及電子線折射影像圖/第6 俜_ T I &晶結晶存在於電解銅箱表面的示意圖。第7圖 妝旦，你θ #泊表面在軟蝕刻（soft etching)後的表面形 顧=雪輊二罢8圖係顯示銅箱迴路剖面的示意圖。第9圖係 楱側面的Ϊ倒面的剖面示意圖。第1 0圖係顯示表面處理 職側面的剖面示意圖。 [符號說明] 1〜電解銅箔； 3〜電解裝置； 5〜錯糸陽極； 7〜微細銅粒； 9〜表面處理機； 11〜粗化處理槽； 1 3〜防銹處理槽； 1 6〜水洗槽。V. Description of the invention (3) When this printed circuit board is used in a motor product, the heat resistance of the ancient part will be high, which will cause the copper foil circuit to rapidly degrade and become damaged. From this result, it can be known that if the printed circuit board is subjected to a slight impact, it will suddenly break the wire, causing the action of the motor products, etc., "The diagram is simply explained:" ". = 1 The diagram shows the schematic diagram of electric copper foil Sectional view. Figure 2 shows a conceptual diagram of the manufacturing process of electric steel & Figure 3 shows a crystal grain size chart of a relatively large family. Figure 4 shows an electrolysis without a double crystal structure. 1 2 3 4 = ^ ΤΕΜ shirt image and electron beam refraction image. Figure 5 shows the TEM image and electron beam refraction image of a decomposed copper box with a double Ξ = / / No. 6 TI TI & crystals exist in electrolysis Schematic diagram of the surface of the copper box. Figure 7: Makeup, your θ #Poor surface after soft etching (snow etched) = Snow 轾 2 strike 8 Figure Schematic showing the section of the copper box circuit. Figure 9 shows 楱A schematic cross-sectional view of the sloping side of the side. Figure 10 shows a schematic cross-section of the side of the surface treatment. [Notation] 1 ~ electrolytic copper foil; 3 ~ electrolytic device; 5 ~ staggered anode; 7 ~ fine copper particles; 9 ~ surface treatment machine; 11 ~ roughening treatment tank; 1 3 ~ anti Rust treatment tank; 16 ~ water washing tank.

1 〜析離箔（銅箔基層） 4〜迴轉陰極； 2 6〜銅箔粗面； 3 8〜粗化面； 4 1 〇〜酸洗處理槽； 12、W〜陽極電極； 15〜乾燥處理部； 4832921 ~ Separation foil (copper foil base layer) 4 ~ Rotary cathode; 2 6 ~ Rough surface of copper foil; 3 8 ~ Roughened surface; 4 1 ~ Pickling treatment tank; 12, W ~ anode electrode; 15 ~ Drying treatment Ministry; 483292

五、發明說明（4) 發明說明： 此，本發明係有關於發明者精心研 阻層和銅箔之間的介面密著性向上提升的妗^否可以將光 本發明的銅箔，不需經表面拋光研 ：‘’如果使兩 層和銅箱之間的介面密著性向上提升。以$」印可將光阻 明。 ’卜砘來說明本發 在申請專利範圍第1項中，一種電解銅 成份的溶液中電解而得，其特徵在於：/雷’在含有銅 面側的結晶具有20%以上的雙晶結構。以解銅箱之光澤V. Description of the invention (4) Description of the invention: Therefore, the present invention relates to the inventor's careful study of the improvement of the interface adhesion between the resistance layer and the copper foil. Surface polishing study: `` If the interface adhesion between the two layers and the copper box is increased upwards. Use "$" to illuminate the photoresist. "Bud to explain the present invention. In item 1 of the scope of the patent application, an electrolytic copper component is obtained by electrolysis in a solution, and is characterized in that: / Ray 'has a double crystal structure of 20% or more in the crystal containing the copper surface side. To unlock the luster of the copper box

接著，為了能輕易了解說明，請來閩第 第3圖件將從銅绪的製造方法到光阻被覆的=圖及 說明。一般上，具有如第丨圖所示剖面構造的耘，仃 由如第2圖所示電解工程和表面處理工程所製造經 二子Λ業領域的印刷電路板製 仏的暴礙柯斜。另外，在第1圖中包括省略未繪出在表 處理工程所形成的防銹層。 土·Then, in order to easily understand the explanation, please come to Fujian. The third picture will be from the manufacturing method of Tongxu to the photoresist coating = diagram and description. In general, a core with a cross-sectional structure as shown in FIG. 仃 is produced by electrolytic engineering and surface treatment engineering as shown in FIG. In addition, the rust preventive layer formed in the surface treatment process is omitted in the first figure. earth·

電解工程，正確來說其實是電解銅箔的基層（bulk)的 製造裝置，在筒狀（drum)的迴轉陰極和沿著該迴轉陰極形 狀對向配置的錯系陽極之間，流動著硫酸銅溶液，然後利 用電解反應使銅在迴轉陰極食的表面析出，該析出的銅是 箔的狀態，接著再從迴轉陰極表面連續剝下銅箔而將之捲 取而成銅箔捲筒。這個階段的銅箔稱為「析離箔」，以下 皆以此名稱稱之，該析離箔就是所謂形成的鈉箔基層。此 時的析離箔由於未經任何的防銹表面處理，所以電解析出Electrolysis engineering is actually a manufacturing device for the base layer of electrolytic copper foil. Copper sulfate flows between a drum-shaped rotary cathode and a staggered anode arranged opposite to the shape of the cathode. The solution was then subjected to electrolytic reaction to precipitate copper on the surface of the rotary cathode. The precipitated copper was in the state of a foil, and then the copper foil was continuously peeled off from the surface of the rotary cathode to be rolled into a copper foil roll. The copper foil at this stage is called "segregation foil", which is hereinafter referred to as this name. This segregation foil is a so-called sodium foil base layer. At this time, the ionized foil is electrolyzed because it has not been subjected to any anti-rust surface treatment.

2169-3598-PF.ptd 第8頁 五、發明說明（5) 後的銅具有活性化的狀態， ^ " 子結合而使該析離羯非常容易常容易與空氣中的氧原 該析冑羯與迴轉電極接 _ 印自鏡面的迴轉電極表面 J離的那-面，由於是複 稱該面為光澤面。相對於此 ^有光澤平滑的表面，获 狀，甴於在每一個結曰、面;出銅2出側，析離猪的表面ς 以會顯示出山形的凹凸狀的結晶成長速度不同，所 拿來應用於與絕緣材料貼合Ί =稱為粗面。而該粒面是 上及以下所述，在使用析離羯的==層&。關於以 面」一詞來說明。 、”候的也明，都以「粗 關於本發明，在雪解 的光澤面來實施的。此時的析離J = j ::對鋼箱 若從表面看，則具有20%以上 迭*的^晶構造， 雙晶構造般地往内部伸#推土蹩日日構把亚且如同表面 項所述，在從7 而且如申請專利範圍第2 貝所述在攸先澤面侧的表面起算5 ^^以士沾、_痒弟2 維持有20%以上的雙晶構造的爷 、’木又，若能 决丄 J古 这疋敢理想的狀觫。m 為在形成蝕刻光阻層之前，必須 〜口 =表面去除卜2…以達到除去防錢元素及表面粗化】 在此’為，了要決定雙晶的存在比例，便以τεμ(穿透形 電子顯微鏡）來觀察，由ΤΕΜ照片中，可確認雙晶構造佔了 ! 多少區域面積’進而推論雙晶構造所佔有的比例。在此為| 了明確地觀察雙晶構造和其他結晶粒之間的邊界，本發明j 是採用10000倍以上的放大倍率，在15/zmM5/zm的狹窄面2169-3598-PF.ptd Page 8 V. Description of the invention (5) The copper has an activated state. The combination of ^ " ions makes the dissociation of tritium very easy and often easy to decompose with the oxygen in the air.羯 Connected to the rotating electrode _ The surface that is printed away from the surface of the rotating electrode surface J of the mirror surface is called a glossy surface because it is duplicated. In contrast to this ^ glossy and smooth surface, it is obtained at each knot and surface; the copper 2 is on the side, and the surface of the pig is isolated. The growth rate of crystals that show a mountain shape is different, so It is used for bonding with insulating materials. The grain surface is described above and below, and the == layer & About the term "face". It is also clear that the designation is based on "the present invention is implemented on the glossy surface of the snow solution. The separation at this time J = j :: If the steel box is viewed from the surface, it has more than 20% overlap * The crystalline structure and the double crystal structure extend towards the inside. # 推土 蹩 日 日 架 把 亚 和 As described in the surface item, the surface on the side of Yoshizenzai from 7 and as described in the patent application scope No. 2 Starting from 5 ^^ Yeshan, _Yi Di 2 The master who maintains a dual-crystal structure of more than 20%, 'Yu You, if you can determine the ideal state of the ancient times. M is the formation of an etching photoresist layer Before, it is necessary to remove the surface = 2 to remove the anti-money element and surface roughening] Here, to determine the proportion of the existence of the double crystal, use τεμ (transmission electron microscope) to observe. In the TEM photo, it can be confirmed that the double crystal structure occupies! How much area area ', and then the ratio of the double crystal structure is deduced. Here is | to clearly observe the boundary between the double crystal structure and other crystal grains, the invention j is With a magnification of more than 10,000 times, on a narrow surface of 15 / zmM5 / zm

483292 五、發明說明（6) 積中觀察，觀察縱狀的結構，確定是雙曰 積要有20%以上的規定。因此這個數笑阳構造的部分的面 值，應被解釋含有一定的測定誤差。太^不忐解釋成絕對 據研究所得的測定誤差，約有一成左二1發明者等，根 析離箔的製造條件中，跟本發明關誤差會發生。 的雙晶構造的電解銅落的製造最為重母f 20/〕以上 專利範圍第2項所述，甴電解工程及矣1°♦。就是，如申請 的電解銅箔的製造方法，其中的電解八^理工^程所構成 筒和沿著迴轉陰極筒的形狀對向配置===迴轉陰極 供給硫酸銅溶液，連續電解而使在迴轉陰= ， T 剝下，且在迴轉陰極筒的銅電解析&面R 用： 晶粒度6· 0號以上的氧化鈦材料。 k罔'、'3 說，迴轉陰極筒的銅電解析出面的氧化鈦 科，其結晶粒度必須是6 〇雖，ri卜。、丄、《 社曰η · ㊉裡所說的「氧化鈦 二=粒度6·〇號以上」，可以用第3圖的氧化鈦結晶粒圖片 « 來判別，結晶粒度的判斷是使用切斷法，以Jis G 〇552所 規定的鋼的肥粒鐵（f err i te)結晶粒度試驗方法的同樣基 準來測定，先以放大1〇〇倍並確認結晶粒，然後在25_平 方中求取結晶粒的平均數，再換算成結晶粒度號 公式如第1式所示， 第1式： 粒度號碼=(Log η / 0.031) + 1 η:在顯微鏡loo倍率下的25_平方中的結晶粒平均數 像之I的氣化欽的結晶粒越細時，使用該氧化欽製；告 II ! _ 1 1 1 I 1 1 2169-3598-PF.ptd ^ ^ —----—- 第10頁 483292 五、發明說明（7) 出來的電解銅箔，就會使從光澤面側的表面起算5 // m以上 深度的雙晶構造的密度提升。因此若沒有達到本發明所定 義之「結晶粒度6. 0號以上」的話，關於本發明的光澤面 側表面就無法具有2〇%以上的雙晶構造，而無法製造出安 疋的銅箔表面。 更者，在申請專利範圍第3項中，有申請專利範圍第2 項所述的電解銅箔的製造方法，其中硫酸銅溶液係添加膠 及/ 或明膠（gelatin)0.2mg〜20mg/L。 谬及明膠，使用市面上的販賣品就復足夠了。例如， 用於食用的明膠也可能拿來使用。膠及明膠的添加可以使 銅箱的伸展率、耐折性等的物理性質得到改善，這是一般 所^的而且膠及明膠一起使用也不會不方便。在此，得 4知的物性改質效果，並對於電解液而言，該膠可當作 ，量的氯，子之供給來源。添加膠及明膠的量，雖然有一 =的誤差里，但可利周含有5000 //g/g〜20000 //g/g程度的 j兀：的性質。關於本發明，使電解液中含有微量的氯元 ΛΛ, 轉陰極筒的銅電解析出面’是使用結晶粒度6. Λ好的材料ΛΛ，所製造出來的析離箱便會有 雙晶組織的促，進是說’ ^素是擔任了促進形成483292 V. Description of the invention (6) Observing in the product, observing the vertical structure, it is determined that the double product must have a requirement of more than 20%. Therefore, the face value of this part of the Xiaoyang structure should be interpreted to contain certain measurement errors. It is not interpreted as an absolute measurement error based on research. About 10% of the inventors on the left, 1 and the like, according to the manufacturing conditions of the separation foil, errors related to the present invention will occur. The production of the electrolytic copper drop with the double crystal structure is the heaviest mother f 20 /] or more. As described in the second item of the patent scope, 甴 electrolytic engineering and 矣 1 ° ♦. That is, as in the manufacturing method of the applied electrolytic copper foil, wherein the barrel formed by the electrolysis process and the shape of the rotary cathode barrel are oppositely arranged, the copper sulfate solution is supplied by the rotary cathode, and the continuous electrolysis is performed to make the Anion =, T is peeled off, and is used in the copper electrolysis & surface R of the rotating cathode tube: Titanium oxide material with a grain size of 6.0 or more. K 罔 'and' 3 said that the crystal size of the titanium oxide branch of the copper electrolysis surface of the rotary cathode tube must be 60%. , 丄, "So Titanium Dioxide =" Titanium Dioxide 2 = Particle Size 6.0 or More "as described in the company, can be judged by the picture« Measured on the same basis as the ferrite grain size test method for steel specified by Jis G 0552. First, magnify by 100 times and confirm the crystal grains, and then calculate the value in 25 square meters. The average number of crystal grains is converted into crystal grain size. The formula is shown in Formula 1: Formula 1: Particle size number = (Log η / 0.031) + 1 η: Crystal grains in 25_ square at the microscope loo magnification The finer the crystal grains of the gasification film of the average image I, use this oxidative filming; report II! _ 1 1 1 I 1 1 2169-3598-PF.ptd ^ ^ —----—- 10th Page 483292 5. The electrolytic copper foil from the description of the invention (7) will increase the density of the double crystal structure with a depth of 5 // m or more from the surface on the glossy side. Therefore, if the "crystal grain size 6.0 or more" as defined in the present invention is not achieved, the glossy surface side surface of the present invention cannot have a double crystal structure of 20% or more, and a safe copper foil surface cannot be produced. . Furthermore, in item 3 of the scope of patent application, there is a method for manufacturing an electrolytic copper foil as described in item 2 of the scope of patent application, wherein the copper sulfate solution is added with gelatin and / or gelatin (0.2 mg to 20 mg / L). In the case of gelatin, it is enough to use commercially available products. For example, gelatin for edible use may also be used. The addition of glue and gelatin can improve the physical properties such as elongation and folding resistance of the copper box. This is generally used and it is not inconvenient to use glue and gelatin together. Here, we know the effects of physical property modification, and for the electrolyte, the glue can be used as a source of chlorine and the amount of chlorine. The amount of gelatin and gelatin added, although there is an error of =, but Keli Zhou contains j: about 5000 // g / g ~ 20000 // g / g: properties. Regarding the present invention, the electrolytic solution contains a small amount of chlorine element ΛΛ, and the copper electrolysis surface of the cathode tube is made of a crystal grain size 6. Λ Good material ΛΛ, the produced separation box will have a double crystal structure Promoting, advancing is to say that ^ prime is serving to promote formation

加旦2 ί t η明的電解銅箔的製•’其膠及/或明膠的添 效^ .另外' 2lDg/L的話，就沒有促進形成雙晶組織的 心，因為二果已該二及:或添加量如果超過2—/ ‘已 '、二飽和，也 >又另更進一步地增加形成 483292 五、發明說明（8) 一~ ----^ 雙晶組織比例的效果。 有雜Ϊ不ί ί十述條件所製造出來的電解銅羯，則不會含 剡=就算是表面含有不到20%的雙晶時，該雙晶延伸 次了二/ m以内的地方就停止了。在第4圖中，是顯示不 / 乂條件所製造出來的析離箔的TEM圖片和電子束反 t，片。然後，在第5圖中，是顯示滿足上述條件所製造 出來的析離箔的TEM圖片和電子束反射圖片。特別是從第4 圖和第5圖的電子束反射圖片來互相比較 > 可清楚地分辨 其。第5圖的電子束反射圖，顯示存在有特定結晶面I 的雙晶結構。另外，第4圖雖然是用3〇〇〇倍的倍率來觀察i ，然而就算是以1 0000倍以上的倍率來觀察，也無法完全 _ 確認雙晶結構。相對地，第5圖中，用1〇〇〇〇倍的倍率來觀 察就可以清楚地確認雙晶結構。第5圖TEM圖片右側的暗區j 可觀察到縱線狀的部位，就是所謂的雙晶結構。 這裡所說的雙晶或雙晶結構，就.是指構成電解銅羯的 銅結晶粒的析出結晶面，即以一定的結晶面當作交界，具 有相互地鏡面對稱的結晶構造。因此，若要以圖面來表示 存在於電解銅箔表面的雙晶結構的分布狀況，則如 所示。 ， 接著，該析離箔在表面處理工程中，進行粗化處理和 防銹處理，形成粗面的粗化處理是在硫酸鋼溶液中，流有p 所謂焦電鍍條件的電流，使微細銅粒析岀而形成具有山形 狀的凹凸粗面；接著以平滑電鍍條件的電流範圍進行被覆 電鍍，以防止微細銅粒的脫落。因&，析出附著微細銅粒Canadian 2 ί t η Ming of the production of electrolytic copper foil • 'the glue and / or the effect of gelatin ^. In addition,' 2lDg / L, there is no heart to promote the formation of a double crystal structure, because the two fruits should be two and : Or if the added amount is more than 2-/ '' saturated ', di-saturated, it will be further increased to form 483292. V. Description of the invention (8) The effect of the ratio of double crystal structure. There is no miscellaneous 的 Electrolytic copper 羯 produced by the ten conditions, it will not contain 剡 = even if the surface contains less than 20% of the double crystal, the double crystal extension will stop within 2 / m Already. In Fig. 4, a TEM image and an electron beam reflection film of the dissociated foil manufactured under the conditions of no / 乂 are shown. Fig. 5 shows a TEM image and an electron beam reflection image of the ionization foil manufactured under the above conditions. In particular, the electron beam reflection pictures of Fig. 4 and Fig. 5 are compared with each other > The electron beam reflection diagram of FIG. 5 shows a double crystal structure having a specific crystal plane I. In addition, in Fig. 4, although i is observed at a magnification of 3,000 times, even if observed at a magnification of 10,000 times or more, the double crystal structure cannot be completely confirmed. In contrast, in Figure 5, the double crystal structure can be clearly confirmed by observation at a magnification of 1,000 times. In the dark area j on the right side of the TEM image in Fig. 5, a vertical line-shaped portion can be observed, which is a so-called double crystal structure. The twin-crystal or twin-crystal structure mentioned here refers to the crystallized surface of the copper crystal grains forming the electrolytic copper alloy, that is, a certain crystal surface is used as a boundary, and the crystal structures are mirror-symmetrical to each other. Therefore, if the distribution of the double crystal structure existing on the surface of the electrolytic copper foil is shown graphically, it is as shown below. Next, in the surface treatment process, the segregation foil is subjected to a roughening treatment and an anti-rust treatment to form a rough surface. The roughening treatment is performed in a sulfuric acid steel solution, and a current of p so-called coke plating condition is passed to make fine copper particles. It is analyzed to form a rough uneven surface having a mountain shape; and then, plating is performed under a current range of smooth plating conditions to prevent the fine copper particles from falling off. &Amp; fine copper particles deposited

------—一~ 五、發明說明（9) 於粗面？過程’就稱為「粗面化」。 接者，在表面處理工衮 ^ 電鍍、鍍鉻處理等的防銹L :之：乾燥鋅合金、路系的 處電解銅'的製造，該電解銅乙;;;鋼;； 此不ίί，通常由於被覆電鍍和防銹處理展” 面 C。在本發明的電_剖面圖；ϊ;的薄’因 覆電鍍層和防銹處理層。 不中便未繪出被 =錄處理層的目的是在於防止表面處呵" 該防銹層存在於鋼箱的表面。g/r使的鋼落氧 馨 就如上述：ίΐ;;;有防錄處理層。 羯 成、，，巴緣層的預浸（ ^解銅箔，經 就做出了各式各樣的銅;)積工/板積接層著熱\成形的工程 過敍刻：程便製造出印刷接考積層板經 目如習知之爭雜。。 工程是從位於銅“：：：刻工程，如以下之說明 始。該整面處理”面的電解銅辖的整面處心刻 行軟勉刻處理；；Γ:下述的2種處理合並使用①L 去，以去除麵π用化學溶解把電解銅羯表面約2,，① 素。②在雷面的污染物、不要的氧化膜以及 去約2 _公桐落表面施以抱光研磨等的物理研；防：元 的鋼箔表面，^可得到銅的乾靜表面，也造成了適杏叙2 性可向上提升而使之後的蝕刻光阻和銅箱之間的介；------— 一 ~ 5. Description of the invention (9) on rough surface? The process' is called "roughening." In turn, the surface treatment process ^ rust prevention of electroplating, chrome plating, etc .: of: the production of electrolytic zinc in dry zinc alloys, road systems; the electrolytic copper B ;; steel; this is not, generally Because the coating is plated and rust-resistant, the surface C is shown in the electrical section of the present invention; the thin layer is because of the plating and rust-resistant layer. The purpose of the coating layer is not shown if it is not correct. It is to prevent the surface from rusting. The rust-preventive layer exists on the surface of the steel box. G / r makes the steel drop oxygen like the above: ίΐ ;; there is an anti-recording treatment layer. Pre-impregnated (^ Uncopper copper foil, made a variety of copper;) Product engineering / board build-up lamination heat \ forming engineering process description: Cheng will produce printed test laminate board The misunderstanding of knowledge ... The project is located in copper "::: engraving project, as explained below. The entire surface of the "coated copper" surface is softly and softly carved; Γ: The following two types of processing are combined and used ①L to remove the surface π and chemically dissolve the surface of the electrolytic copper 羯 about 2 ,, ① prime. ② Physical research on the surface of the mine, unnecessary oxide film, and polishing, etc. _ Gongtong Luo surface, polishing, etc .; prevention: Yuan steel foil surface, ^ can get copper dry The static surface also caused the compatibility between the second photoresist and the copper box to be improved upwards;

結晶粒的雙m?;銅箱的光澤面表層，當沒有銅 過軟钱刻處理有不到2°%的雙晶時’若不經 路時光阻和鋼心就無法破保在形成微細迴 j< 間的介面密著性。 含有二〜地上’Λ於曰本發明的電解銅落，該銅猪的表面層，Double m? Of crystal grains; the surface of the glossy surface of the copper box, when there is no copper too soft, and less than 2 °% of the double crystals are engraved. The interface adhesion between j <. Containing two to the ground, the electrolytic copper drop of the present invention, the surface layer of the copper pig,

,^ 、又E日結構，因此不需要上述的物理研磨C 在形上電解銅箱，只需要作軟蝕刻處理，就能確保 姓刻處理的目L二的介面密著性。因為軟 除方防銹兀素，所以不能省略。 阻二：=:後表層形成㈣1光 體弁阳娇搂士 "〜尤疋被所明的乾潯膜、電著光阻、液 光、顯與等产理^後該钱刻光阻層再經重疊圖案薄膜、曝 刻光阻層浸潰於驗性溶液内一段時間。曝=餘 之間的介面密著性有顯著問題的時候解鋼荡 ::落表面的㈣光阻層，⑨會有從銅箱表； 發生。另夕卜，即使沒有剝離現象，在銅落 J離的現象 層有部分浮起現象的話，因為無法充分發揮餘列$刻X阻 作用，使得在蝕刻工程時，在蝕刻光阻層下方j光阻層的 ，因而產生迴路斷線的情況發生。 e 的鋼箔溶解 在此，關於本發明的含有2 〇%以上雙晶結 箔的鋼箔積層板，和未含有2 〇 %以上雙晶結構的的電解銅 的銅箔積層板做比較，其銅箔和蝕刻光阻層間' 電^解鋼箔 評價結果如第1表所示。在此的整面處旦 、费著性的 " 不必作物理, ^, And E-day structure, so the physical grinding of the above-mentioned electrolytic copper box is not required. Only soft etching is required to ensure the interface adhesion of the last name. It cannot be omitted because it is a rust preventive element. Resistance 2: =: The back surface layer is formed by a photoresist, and the photoresist layer is formed by a dry film, electrophotographic photoresist, liquid light, display, and so on. Then immersed in the test solution for a period of time by overlapping the pattern film and the exposed photoresist layer. When there is a significant problem with the interface adhesion between exposure = Yu, the solution of steel slag :: the surface of the photoresist layer on the surface, there will be from the copper box; In addition, even if there is no peeling phenomenon, if there is a partial floating phenomenon in the copper layer and the phenomenon layer, because the remaining X-cut X-resistance function cannot be fully exerted, during the etching process, the light under the etching resist The resistance layer, and thus the circuit disconnection occurs. The steel foil of e is dissolved here. As for the steel foil laminated board of the present invention that contains more than 20% of the double-crystal junction foil, and the copper foil laminated board that does not contain electrolytic copper of more than 20% of the double-crystal structure, its Table 1 shows the evaluation results of the electrolysis of the copper foil and the etched photoresist layer. The whole thing here is costly " no need to do physics

2l69-3598.PF.ptd 第14頁 483292 五、發明說明αι) ^ 研磨的處理’只要在1級濃硫酸溶液4〇ml/L、3〇%雙氧水 3 2m 1/L的所謂硫酸-雙氡水系中，進行軟蝕刻處理。之後 ，水洗乾爍後，進行姓刻光阻層的處理，也就是說使用日 合A 1 u ί 〇 (譯音）株式會社的紫外線硬化形的乾薄膜，在電 解銅、冶表面形成薄片（laminate)，益使周圖案薄膜（ pattern-film)作成線·路寬度3〇 '線間空隙1〇〇 的 1 30 /z m間距的梳形迴路，之後再經曝光、顯影，就形成為 了形成迴路的蝕刻光阻層圖案。然後再甩2 5倍的顯微鏡來 觀察剝離狀況，以及用TESA膠帶來測試觀察其剝離狀況。 第1表 試料 乾溥族密著性試驗結果 — 試驗方法" —試驗方法2林二 j有20¾雙晶結構的電 解鋼综的鋼楚稍層板 0/30 0/30 — i有10¾雙晶結構的電 解鋼综的銅综稍層板 [2/30 18/30 — 不含雙晶結構的電解銅 箔的銅箔積層板 21/30 28/30 — 。觀察30個 端部有剝離 *試驗方法1 :周25倍的顯微鏡來觀察剝離狀況 試料，把有完全剝離以及可以確認乾薄膜的緣 現象的試料個數紀錄下來。 **試驗方法2 :兩20mm寬度的TESA膠帶，黏在梭形、回 面的乾薄膜上，並且在水平方向拉扯了]£^膠帶' ^、路表 乾薄膜黏在TESA膠帶與乾薄膜的接著面侧的試料把有 下來。觀察30個試料的結果。 ’ ^數紀錄2l69-3598.PF.ptd Page 14 483292 V. Description of the invention αι) ^ Grinding treatment 'As long as the first-grade concentrated sulfuric acid solution 40ml / L, 30% hydrogen peroxide 3 2m 1 / L of the so-called sulfuric acid-bisamidine In the water system, soft etching is performed. After that, it was washed with water and dried, and then the photoresist layer was engraved. That is to say, a UV-curable dry film of Nippon A 1 u ί (transliteration) Co., Ltd. was used to form a laminate on the surface of electrolytic copper and metallurgy. ), The pattern pattern film (film-film) is made into a comb-shaped loop with a line and road width of 30 'and a gap of 100 between lines and a pitch of 30 / zm, and after exposure and development, it is formed to form a loop. Etching the photoresist layer pattern. Then shake the microscope 2 to 5 times to observe the peeling condition, and use TESA tape to test and observe the peeling condition. Table 1 Sample test results for the dryness of the Qiang ethnic group—Test method " —Test method 2 Lin Erj, a thin layer of electrolytic steel heald with a 20¾ dual crystal structure, 0/30 0/30 — i has 10¾ pairs Copper heald laminates for electrolytic steel healds with crystalline structure [2/30 18/30 — Copper foil laminates without electrolytic copper foil with double crystal structure 21/30 28/30 —. Observation of peeling at 30 ends * Test method 1: 25 times a week to observe the peeling condition of the sample. Record the number of samples that have completely peeled off and can confirm the edge phenomenon of the dry film. ** Test method 2: Two 20mm wide TESA tapes are stuck on the shuttle-shaped, backside dry film and pulled in the horizontal direction] £ ^ Tape '^, road surface dry film is stuck on the TESA tape and the dry film Then the sample on the front side is removed. Observe the results of 30 samples. ’^ Number record

2169-3598-PF.ptd 第15頁 4832922169-3598-PF.ptd Page 15 483292

1含有20%雙晶結構的電解 中’電解銅箔表面的乾薄 生，而且在TESA膠帶實驗 因此可了解該條件的乾薄 而且也可了解「未含有雙 」的乾；4膜和銅落間有最 五、發明說明（12) 由第1表可以清楚地發現， 銅箔的銅箔積層板」的3 〇個試料 膜沒有從銅箔表面剝離的現象發 中’乾薄膜也沒有黏在膠帶側， 丨膜和銅箔間有相當好的密著性。 晶結構的電解銅箔的銅箔積層板 差的密著性。 這個現象是因為有含雙晶和不含雜曰， 會使電解銅箱表面產生不同的微細二， 有顯示含有2。%雙晶結構的電解鋼羯的銅』積圖：有 10%雙晶結制電解銅镇的銅箱積 及；：t 銅㈣層板，在心刻=的V·: ;;ί=;凸狀。這些是臟(掃描式電子顯微鏡)觀察 =7圖可確認，電解銅箱表面含有的雙晶結構比例 J夕：：，軟餘刻後的銅羯表面也就有越多的微細凹凸形 ，二=此，雙晶比例若有如本發明所說的20%以上的話， 後綱表面也就有很多的微細凹凸形狀，不需 =仃物理研磨，就可W保銅光阻層之間的密 阻層形成後，就要進行 以形成印刷電路。此時 的密著性的指標方法是 的迴路寬度是否有變化 在印刷電路板工程中的蝕刻光 餘刻銅的工程，把多餘的銅除去， ’要來表示銅箔和蝕刻光阻層之間 ’欲形成的迴路寬度和實際做出來 483292 ~一 I 一 五、發明說明（13) 二，8圖為顯示銅蝕刻後的迴路斷 又匕括迴路斷面的上面的寬度 不意圖，迴路寅 接觸的底面的寬度（第8圖中的b)。的W，以及跟基材 底面的寬度跟欲形成的迴路寬度_，，亡，上面的寬度和 ，深寬比（aspect ratio)越好，^疋取好的。也就是誃 關於本發明，因λ要研究銅落：：2性越好。“ 著性，所以不希望用銅蝕刻液的組 ζ光阻層之間的密 法等等其他原目來作為判斷深寬比的^ 2液的組成方 較蝕刻光阻層上的迴路寬度和迴路面二:。在此，比 ^的Ο ’以此寬度差來作為研究。_結果如 =，迴'寬度作為目的來形成钱刻光阻層上； :=ί寬度’同時地曝产顯影的接果，關於所有的試料 斤k 4見度是29· 3 /zm。還有，在此所使周的全部電解銅 箔的公稱厚度是18 /zm。 | \ 第2表 試鞞 蝕到光阻層上的迴 路的實測寬度(μιη) 銅蝕到後的迴路上 面的實測寬度(μηι) 含有20%雙晶結構的電 解銅综的銅结稍層板 29.3 28.4 含有10。/。變晶結構的電 解銅箔的飼箔種層板 23.7 不含雙晶結搆的電解銅 箔的舸箔積層板 20.8 銅姓刻條件：硫酸銅溶液1 In the electrolysis containing 20% double crystal structure, the dryness of the surface of the electrolytic copper foil can be understood, and in the TESA tape experiment, the dryness of the condition can be understood and the "non-containing double" can be understood; 4 the film and the copper fall Fifth, the description of the invention (12) From the first table, it can be clearly found that 30 samples of the copper foil copper foil laminates did not peel off from the surface of the copper foil, and the dry film did not stick to the tape. Side, there is quite good adhesion between the film and the copper foil. Laminated copper foil of electrolytic copper foil with a crystalline structure has poor adhesion. This phenomenon is due to the presence of double crystals and no impurities, which will cause different microseconds on the surface of the electrolytic copper box. % Double-crystal structure of copper in electrolytic steel 积 product: copper box with 10% double-crystal junction electrolytic copper town; t copper ㈣ laminate, carved in the heart = V ·: ;; ί =; shape. These are dirty (scanning electron microscope) observations = 7. It can be confirmed that the proportion of the double crystal structure contained on the surface of the electrolytic copper box is J ::, the softer the surface of the copper cymbal, the more fine unevenness. = Here, if the ratio of the twin crystal is more than 20% as mentioned in the present invention, the surface of the posterior gangue will also have a lot of fine uneven shapes. Without physical grinding, it is possible to maintain the tight resistance between the copper photoresist layers. After the layer is formed, it is performed to form a printed circuit. The index method of adhesion at this time is whether there is a change in the width of the circuit. In the printed circuit board project, the copper is etched and the extra copper is removed, and the extra copper is removed. 'The width of the circuit to be formed and actually made 483292 ~ I I. Fifth, the description of the invention (13) II, 8 The picture shows the width of the circuit after copper etching and the upper width of the circuit cross section is not intended, the circuit is in contact The width of the bottom surface (b in Figure 8). W, and the width of the bottom surface of the substrate and the width of the circuit to be formed, the better the upper width and the aspect ratio, the better. That is, 誃 About the present invention, because λ has to study the copper drop: 2: the better. "It is not desirable to use the dense method between the group ζ photoresist layer of the copper etchant and other original purposes as the composition of the ^ 2 solution to determine the aspect ratio than the circuit width on the etch photoresist layer and Circuit surface 2: Here, the ratio of ^ 'is used as the width difference for research. _Results such as =, return to' width as the purpose to form a money-etched photoresist layer;: = ί width 'simultaneously expose and develop For all samples, the visibility of all the sample k 4 is 29 · 3 / zm. In addition, the nominal thickness of all electrolytic copper foils used here is 18 / zm. | Table 2 test erosion Measured width of the circuit on the photoresist layer (μιη) Measured width of the circuit after copper etching (μηι) Contains 20% double-crystal structure of electrolytic copper healds with copper junction layer 29.3 28.4 Contains 10% Feeding foil seed board of electrolytic copper foil structure 23.7 Laminated foil laminated board without electrolytic copper foil of double crystal structure 20.8 Copper name engraving conditions: copper sulfate solution

2169-3598-PF.pte 第17頁 483292 五、發明說明（14) 測長方法：使用光學式測長機 由第2表可得知，「含有2〇%雙晶結構的電解銅箔的銅 邊積層板」的時候，蝕刻光阻層上的迴路的實測寬度和銅 钱刻後的迴路上面的實測寬度相差最少。也就是因為電解 鋼猪表面和蝕刻光阻層之間的密著性很好，所以銅蝕刻液 报少流入電解銅箔和蝕刻光阻層之間，而不會蝕刻到需留 下的銅羯。另外，此時用各種銅箔積層板來製造梳形圖案 的迴路底面的實測寬度範圍是31〜31· 5 /zm，可確認蝕刻程 度沒有什麼差異。 由 在設計 品實裝 線部的 因 結構的 钱刻工 成本。 提升了 刷電路 發明的 於運到 迴路時 時的實 領域面 此’如 電解銅 程的整 並且因 5所以 板的製 實施例 了蝕刻的 ，就可以 裝可能領 積，而更 申請專利 、冶的銅謂 面處理的 為電解銅 微細間距 造良率大 精度與迴路寬度相近的g的，因此 不用作預測钱刻誤差的設計；在部 域中’也可以確保依照設計的橫格 提焉了部品實裝時的接續信賴性。 範圍第4項所述，使用含有20%雙晶 積層板的話，該銅箔積層板，關於 ，理研磨可以省去，而可降低工程 箔表面和蝕刻光隍層之間的密著性 迴路的形成便得容易了，而使得印 幅地提升。 以下依據第1圖、第9圖及第1〇圖來 電解銅箱之製造方法，以及該製造方法二=本發明之 ，應用於鋼箔積層板的實施例狀態。評俨：3的電解銅箔 >、、、$果如上述的同2169-3598-PF.pte Page 17 483292 V. Description of the invention (14) Length measurement method: According to Table 2 using an optical length measuring machine, "Copper containing electrolytic copper foil with 20% double crystal structure In the case of an "edge-laminated board", the measured width of the circuit on the photoresist layer and the measured width of the circuit after the copper coin engraving have the smallest difference. That is, because the adhesion between the surface of the electrolytic steel pig and the etched photoresist layer is very good, the copper etching solution flows less between the electrolytic copper foil and the etched photoresist layer, and does not etch to the copper 需. In addition, at this time, the measured width of the bottom surface of the circuit using various copper foil laminates to make a comb-shaped pattern was 31 to 31 · 5 / zm, and it was confirmed that there was no difference in the degree of etching. The construction cost is engraved by the money in the structure of the design product assembly line. The actual field of the brush circuit invention is improved when it is transported to the circuit. If the electrolytic copper process is integrated and the board is etched because of the 5th embodiment, the potential can be installed, and a patent and metallurgical process can be applied. The copper surface is processed by electrolytic copper with a fine pitch and a high yield. The accuracy is close to the circuit width, so it is not used as a design for predicting money-cutting errors. In the region, it can also ensure that the design is based on the horizontal grid design. Reliability when parts are mounted. As described in the fourth item of the scope, if a 20% double crystal laminated board is used, the copper foil laminated board can be omitted for physical polishing, and the adhesion circuit between the surface of the engineering foil and the etching layer can be reduced. The formation is easy, and the printing space is improved. The following describes the manufacturing method of the electrolytic copper box according to Figures 1, 9, and 10, and the second manufacturing method of the present invention is applied to the state of the steel foil laminate. Comment: 3 electrolytic copper foil > ,,, $

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樣結果。 ^ 、电解銅羯是經過電解工程A和表面處理工程B所製造出 ，的’關於本發明的電解銅箔1也是用同樣的方法順序來 製造。 目先’關於電解工程A的說明如下述。電解工程a是製 t 電路成加工時·，當作電流導體的電解銅箔1的析離 ^ (、銅，基層）2。電解裝置3是，在筒狀的迴轉陰極4和沿 \ ^ :極4的形狀對向配置的錯系陽極5之間，流動著硫 酉文銅/合/次’然後利用電解反應使銅在迴轉陰極4的筒的表 面析出該析出的銅是箔的狀態，再從迴轉陰極4表面連 續剝下銅箱而將之捲取而成銅箔捲筒。此時迴轉陰極4的 銅的析出面係採周結晶粒度7· 1號的氡化鈦板。 在電解工程A所使用的電解溶液中，含有硫酸銅 (CuS04 ·5Η2Ο)280 〜360g/l、硫酸 1〇〇 〜i5〇g/i、膠Like results. ^ The electrolytic copper tin is manufactured by electrolytic process A and surface treatment process B. ′ The electrolytic copper foil 1 of the present invention is also manufactured by the same method and sequence. The first description of the electrolytic process A is as follows. Electrolysis process a is the separation of electrolytic copper foil 1 (copper, base layer) 2 as a current conductor when processing a t-circuit. The electrolytic device 3 is such that a sulphur copper / combined / time 'flows between a cylindrical rotating cathode 4 and a staggered anode 5 arranged opposite to each other along the shape of the electrode 4. Then, an electrolytic reaction is used to make copper The deposited copper was deposited on the surface of the drum of the rotary cathode 4 in the state of a foil, and the copper box was continuously peeled off from the surface of the rotary cathode 4 and rolled up to form a copper foil roll. At this time, the copper precipitation surface of the rotary cathode 4 is a titanium halide plate having a perimeter crystal grain size of 7.1. The electrolytic solution used in electrolytic process A contains copper sulfate (CuS04 · 5Η20) 280 to 360 g / l, sulfuric acid 100 to i50 g / i, gel

0·2〜20mg/l的酸性硫酸銅溶液。而且以溶液溫度約5(pc、 電流兹度50〜l〇〇A/dm2的條件連續電解而捲取成捲筒 (roll)形狀的析離羯2。在此，以硫酸銅（CuS〇4 · 5H2〇) 360g/l、硫酸I50g/1、膠3mg/1、溶液溫度49它、電流密 度lOOA/dm2為條件，製造應用於公稱厚度18//^的電解銅 猪1的析離箱2，。此時的析離箱2，由於未經任何的防錄表 面，理，所以電解析出後的鋼具有活性化的狀態，因此非 常容易與t氣中的氧原子結合而使該析離箱非常容易氧 接著，該析離泊2，在表面處理工程6進行粗面6的粗An acidic copper sulfate solution of 0.2 to 20 mg / l. In addition, the solution was continuously electrolyzed under the conditions of a solution temperature of about 5 (pc, and a current of 50 to 100 A / dm2, and was then rolled into a roll-shaped dissociation ion 2. Here, copper sulfate (CuS04) was used. · 5H2〇) 360g / l, sulfuric acid I50g / 1, gum 3mg / 1, solution temperature 49 °, current density 100A / dm2 as conditions, manufacturing an isolation box 2 for electrolytic copper pigs 1 with a nominal thickness of 18 // ^ Since the separation box 2 at this time is not provided with any anti-recording surface, the steel after electrolysis has an activated state, so it is very easy to combine with the oxygen atoms in t gas to make the separation. The box is very easy to oxidize. Then, the separation 2 is roughened in the rough surface 6 in the surface treatment process 6.

2169-3598-PF.ptd 第19頁 483292 發明說明（16) 化處理和防錢處理。粗面6的粗化處理是在硫酸銅溶 '夜 中’流動著焦電鏡條件的電流，在粗面6的凹凸表面上析 出附著微細鋼粒7，接著以平滑電鍍條件的電流範圍來進2169-3598-PF.ptd Page 19 483292 Description of the invention (16) Chemical treatment and anti-money treatment. The roughening treatment of the rough surface 6 is performed by flowing a current under the conditions of a coke microscope in a copper sulfate solution at night, and the fine steel particles 7 are deposited on the uneven surface of the rough surface 6. Then, the current range is smoothed under the conditions of plating.

行被後電锻’防止微細銅粒7脫落。因此’以下所述，太 I 粗面6的表面上析出附著微細銅粒7的事就以「粗化面8 j 來稱之。 」 |Post-forging electro-forging 'prevents the fine copper particles 7 from falling out. Therefore, as described below, when the fine copper particles 7 adhere to the surface of the too rough surface 6 are called "roughened surface 8 j." |

β I Μ接著’在表面處理工程Β中，進行完成粗化處理的析 離、冶2雙面的鋅、鋅合金、鉻系的電鍍、鍍鉻處理等的防 ，，理’之後乾燥，捲取成銅箔捲，就完成了電解銅辖的 製造。以下就表面處理工程作詳細的說明。 表面處理工程Β’如第1Q圖的剖面示意圖所示，捲出 j· 的析離箔2 ’在表面處理機9中蛇行地前進。以下就構 面處理機9的各槽，依順序來說明其製造條件。 捲，的析離箔2最初是進入酸洗處理槽1 0。酸洗處理 11 f内疋叙滿了濃度1 5 0 g / 1、液溫3 0 °C的稀硫酸溶液，浸 1 間30秒’把附著在析離箔2表面的油脂成分除去的同 蚪，^把多餘的表面氧化膜除去。 、 仗酸洗處理槽1 0出來的析離箔2，為了要在析離箔2表 广成微細銅粒7，所以要進入粗化處理槽丨丨。粗化 附#梓 ~理疋’要在析離落2表面形成微細銅粒7的析出 _ #者曰11 A ’以及防止微細銅粒7脫落的被覆槽丨丨b所構 # ® Ϊ析離箔2表面形成微細銅粒7的析出附著槽11A，是 )丨l酉文銅洛液，以濃度1〇〇g/1硫酸、18g/1鋼、溶液溫β I Μ Next, in the surface treatment process B, the separation of the roughening treatment, the two-sided zinc, zinc alloy, chromium-based plating, and chrome plating treatment are carried out, and then dried and coiled. Into a copper foil roll, the manufacture of electrolytic copper is completed. The surface treatment process is described in detail below. In the surface treatment process B ', as shown in the schematic cross-sectional view in FIG. 1Q, the separation foil 2' rolled up j · is advanced in a meandering manner in the surface treatment machine 9. Hereinafter, the manufacturing conditions of each tank of the surface treatment machine 9 will be described in order. The volume of the separation foil 2 is initially entered into the pickling treatment tank 10. The pickling treatment 11 f is filled with a dilute sulfuric acid solution at a concentration of 150 g / 1 and a liquid temperature of 30 ° C, and immersed for 1 30 seconds to remove the oil and fat components attached to the surface of the separation foil 2 ^ Remove the excess surface oxide film. In order to form the fine copper particles 7 on the separation foil 2 by the separation foil 2 coming out of the pickling treatment tank 10, it is necessary to enter the roughening treatment tank. Roughening attached # 梓 ~ 理 疋 'to form the precipitation of fine copper particles 7 on the surface of the precipitation 2 # # 者 说 11 A' and the coating groove to prevent the fine copper particles 7 from falling off 丨 丨 #constituted # ® Ϊ dissociation The deposition attachment groove 11A of the fine copper particles 7 was formed on the surface of the foil 2; yes) l 酉 wentongluo liquid at a concentration of 100 g / 1 sulfuric acid, 18 g / 1 steel, solution temperature

五、發明說明（17) 度25。(：、電流密度lOA/dm2的焦電鍍條件電解⑽少。此 時’平板的陽電極1 2 ’相對於析屮糾益 ^ m门一 T、祈出附者微細銅粒7的析離 治2的面’如第1 0圖所示地平行配置。 在田銅粒7脫落的被覆槽11β，是使用硫酸 液，以滾度lDOg/i硫酸、65g/1銅、溶液溫度45t、電流 费度15A/dm2的平滑電鍍條件電解2〇秒。此時，平板的陽 電極12，相對於析出附著微細銅粒7的析㈣2的面，如第 1 0圖所示地平行配置。 m 防銹處理槽1 3，是採用防銹元素的鋅來做防銹處理。 在此槽，以鋅板作為陽電極，當作溶解性陽極丨4，豆目的 ，於維持防銹處理槽13内的鋅濃度平衡。在此的電解條件 是使用硫酸鋅溶液，維持濃度7〇g/ i硫酸、2〇g/1辞的濃 度平衡’並以溶液溫度4〇°c、電流密度i5A/dm2的平滑電 鑛條件電解1 0秒來進行電解工程。V. Description of the invention (17) Degree 25. (:, Electrolysis conditions of coke plating conditions with current density lOA / dm2 are less. At this time, 'plate anode electrode 1 2' is better than the analysis of 屮 ^ m gate one T, praying for the attachment of fine copper particles 7 The surface 2 of 2 is arranged in parallel as shown in Fig. 10. In the coating groove 11β where the copper particles 7 fall off, a sulfuric acid solution is used, with a rolling degree of 1DOg / i sulfuric acid, 65g / 1 copper, a solution temperature of 45t, and a current charge. Electrolysis was performed for 20 seconds at a smooth plating condition of 15A / dm2. At this time, the anode electrode 12 of the flat plate was arranged in parallel to the surface of the precipitate 2 on which the fine copper particles 7 were deposited as shown in Fig. 10. m Rust prevention The treatment tanks 1 and 3 use zinc, which is a rust-proof element, for anti-rust treatment. In this tank, a zinc plate is used as an anode electrode as a dissolving anode, and the purpose of the beans is to maintain the zinc in the rust-proof treatment tank 13 Concentration balance. The electrolytic conditions here are using a zinc sulfate solution, maintaining a concentration balance of 70 g / i sulfuric acid, 20 g / 1, and smoothing electricity at a solution temperature of 40 ° c and a current density of i5A / dm2. Mining conditions electrolyze for 10 seconds to perform the electrolytic process.

防錄處理完成後，析離箔2在乾燥處理部1 5，經由電 熱器110 °C的氣氛溫度，在爐内加熱40秒再通過，而完成 18/zm厚的電解銅箔i，之後再將其捲取成捲筒狀。在以上 工程的析離箔2，在表面處理機9内行進的速度是2· Om/miη 丄而且各槽的每個工程間，設計有水洗槽i 6，以防止帶入 前一槽的使甩溶液。 接著以該電解銅箔1，利用熱壓成形法把電解銅箔的 粗面6貼附在1〇〇 //m厚的FR —4基材上，以製造50cm角的兩 面銅箱積層板，並作前述的第1表及第2表的特性評價。其 測試結果，在乾薄膜密著性試驗中，用同一批内不同位置After the anti-recording process is completed, the separation foil 2 is heated in the furnace at a temperature of 110 ° C for 40 seconds in the drying treatment section 15 and then passed through the furnace to complete the electrolytic copper foil i with a thickness of 18 / zm. Take it up into a roll. In the above process, the separation foil 2 travels in the surface treatment machine 9 at a speed of 2 · m / miη. Moreover, each process room of each tank is designed with a washing tank i 6 to prevent the use of the previous tank. Shake the solution. Next, the rough surface 6 of the electrolytic copper foil was attached to a 1000 // m-thick FR-4 substrate with the electrolytic copper foil 1 by a hot press forming method to produce a double-sided copper box laminate with a 50 cm angle. The characteristics of the first and second tables were evaluated. The test results, in the dry film adhesion test, using different positions in the same batch

483292 五、發明說明（18) 的試片_，以前述試驗方法1及試驗方法i測試2〇點，顯影後 的乾薄膜迴路的緣端部並沒有剝離，TESA膠帶實驗也沒有 問。進打銅初 告】、七目、 〜I』然人诞造跟刖遠同樣的1 30 // m間 距的梳形迴路，對於目標迪歆* d 。m _ ή 标呀路見度30 //m，本實施例得到 平均29·1 //mi度的銅箔迴路。 發明效果483292 V. Test piece of the invention description (18) _ Tested at 20 points by the aforementioned test method 1 and test method i. The edge of the dry film circuit after development did not peel off, and the TESA tape test was not asked. A preliminary report on the advancement of copper], Qimu, ~ I ", the birth of a comb circuit with a distance of 1 30 // m is the same as that of Yuan Yuan. For the target Di 歆 * d. m _ price is marked with a road visibility of 30 // m. In this embodiment, an average copper foil circuit of 29 · 1 // mi degree is obtained. Invention effect

目於本發，電解銅羯，拿來製作銅辖積層板，可以 衣作出精密圖茶（fine pattern)的印刷電路板，可以得到 與目標相近的迴路寬度，迴路設計也變容易了，在部品竇 裝時，部品和迴路之間的接續信賴性也提高τ。從製造^ 程面來看，關於蝕刻工程的整面處理的物理研磨也可以省 略’因此由於工程的削減而可降低成本。更重要的是，因 為蝕刻光阻廣和電解銅領之間的密著性向上提升，而使細 小間距迴路”形成變容易了，而使印刷電路板的製造良率 大幅地向上权升。For the purpose of this article, electrolytic copper tin is used to make copper laminated boards, which can be used to make printed circuit boards with fine patterns. The circuit width close to the target can be obtained, and the circuit design has become easier. When the sinus is installed, the reliability of the connection between the component and the circuit is also improved. From the manufacturing process point of view, the physical polishing of the entire surface treatment of the etching process can also be omitted ', so the cost can be reduced due to the reduction of the process. More importantly, because the adhesion between the etched photoresist and the electrolytic copper collar has increased, the formation of fine-pitch circuits has become easier, and the manufacturing yield of printed circuit boards has been greatly increased.

Claims (1)

/、、申請專利範圍 1· 一種電 其特徵在 該電解鋼 構。 2· 一種電 所述的電解銅 解硫酸銅溶液 理及防銹處理 其特徵在 電解工程 對向配置的不 而使在迴轉陰 銅電解析出面 3·如申請 法，其中該硝 者。 解鋼箱， 於： 箔之光澤 解銅箔的 箔的製ά 而製造出 甩之表面 於： 是在迴轉 溶性陽極 極上電析 ，使用結 專利範圍 酸銅溶液 的電解鋼落 種銅箔積層板 在3有輞成份的溶液中電解而得， 面 1則 α '、、〇 3日具有2 0 %以上的雙晶結 贺：告古、 : 决，如申請專利範圍第1項 #包括：在電解工程中，由電 二*名，再將該析離箔施以粗化處 處理工程； 处 陰極筒聋〇沿莫兮·、 之門，徂1 轉陰極筒的形狀 之h 洽硫酸鋼溶液，連續雪 出的銅箔剥下，曰少、Μ Z~ 曰邺声6 η缺 且在迴轉陰極筒的 曰"立度:唬以上的氧化鈦材料。 第2項料的電解銅羯的製造方 係添加膠及/或明總η〇 ^ 及明尊>〇·2mg〜2〇mg/L ，使用如申請專 月寻利乾圍第1項所述/ 、、 Scope of patent application 1 · A type of electricity characterized by the electrolytic steel structure. 2. An electrolytic copper electrolytic copper sulphate solution treatment and anti-rust treatment, which is characterized by the opposite configuration of the electrolytic project and the appearance of the electrolytic analysis in the rotating cathode. 3. The application method, in which the nitrate. The solution box is: the gloss of the foil and the production of the copper foil. The surface is made of: it is electrolyzed on a rotary soluble anode, and the electrolytic copper plated with a patented acid copper solution is used to seed the copper foil laminate. It is obtained by electrolysis in a solution with 3 rim components. Surface 1 α ′ ,, on the 3rd, has more than 20% of the double crystal knots. Congratulations,: No, if the scope of the patent application # 1 includes: In the electrolysis project, the name of Dian Er * was applied to the roughening treatment process; the cathode tube was deaf. Along the door of Mo Xi ·, 徂 1, the shape of the cathode tube was turned into a sulfuric acid steel solution. The copper foil that is continuously snowing is peeled off, titanium oxide material that is less, Mz ~, snoring 6 η is missing, and is in the rotating cathode tube. The manufacturing method of the electrolytic copper tin of the second item is to add glue and / or Mingzong η〇 ^ and Mingzun > 0.2mg ~ 20mg / L. Describe 2l69-3598-PF.ptd2l69-3598-PF.ptd 第23頁Page 23